EP0344053A1 - Verfahren zur Erzeugung von Hochreinem Wasserstoff durch katalytische Reformierung von Methanol - Google Patents

Verfahren zur Erzeugung von Hochreinem Wasserstoff durch katalytische Reformierung von Methanol Download PDF

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Publication number
EP0344053A1
EP0344053A1 EP89401396A EP89401396A EP0344053A1 EP 0344053 A1 EP0344053 A1 EP 0344053A1 EP 89401396 A EP89401396 A EP 89401396A EP 89401396 A EP89401396 A EP 89401396A EP 0344053 A1 EP0344053 A1 EP 0344053A1
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Prior art keywords
methanol
hydrogen
carbon dioxide
reaction
reaction zone
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EP89401396A
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English (en)
French (fr)
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EP0344053B1 (de
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Daniel Durand
Adrien Orieux
Philippe Courty
Serge Mouratoff
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IFP Energies Nouvelles IFPEN
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
    • C01B3/32—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide or air
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification
    • C01B3/52—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification by contacting with liquids; Regeneration of used liquids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
    • C01B3/50—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen-containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/16—Hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/504—Carbon dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
    • B01D53/047—Pressure swing adsorption
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0415—Purification by absorption in liquids
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465—Composition of the impurity
    • C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2

Definitions

  • the present invention relates to a process for the production of hydrogen by catalytic steam reforming of methanol. This process makes it possible to produce hydrogen of high purity, which can reach or exceed 99.99%, and with a yield, relative to methanol, which can reach or exceed 95%, as defined below.
  • the production of hydrogen from methanol is based on the well-known reaction (FR-1549 206 and 1599 852) of catalytic reforming of methanol with steam: CH3OH + H2O ⁇ CO2 + 3H2 (1) which can be considered as the sum of CH3OH ⁇ C0 + 2H2 (2) and CO + H2O ⁇ CO2 + H2 (3) reaction (2) being the reverse of that of synthesis, and reaction (3) being that of conversion of CO to steam.
  • the hydrogen yield defined with respect to reaction (1), is defined by equation (4) where H2 and CH3OH are respectively the number of gram molecules of hydrogen produced and methanol reacted.
  • the methanol steam reforming reaction can be carried out in the presence of any of the catalysts already proposed for the methanol synthesis reactions.
  • the reforming operation is carried out at temperatures generally between 150 and 350 ° C, preferably between 250 and 350 ° C, under pressures between 0.5 and 10 MPa, preferably between 1 and 5 MPa and with water / methanol molar ratios of between 1 and 10 and preferably between 1.5 and 5. It is possible to operate in the gas phase or in the presence of a liquid phase consisting, for example, of a hydrocarbon or a hydrocarbon fraction by weight specific between 0.65 and 0.90.
  • the reaction catalyst can be a conventional solid catalyst for the high pressure synthesis of methanol for example (Cr-Zn) or low pressure, for example of copper associated with zinc and / or iron and at least one metal M chosen from the group of aluminum and / or chromium.
  • These catalysts are generally in the form of mixed oxides or of the mixture in various proportions of the simple constituent oxides.
  • These catalysts can be packaged either in mass elements, that is to say constituted by oxides of the active elements, or in supported elements.
  • their binders or their supports can for example be silica, alumina, the mixture of these two materials, or a more complex material such as aluminates with a spinel structure (magnesium, zinc, iron or cobalt aluminate) or a perowskite structure ( rare earth aluminate with atomic numbers 57 to 71 inclusive) or even be made up of mixed oxides based on zirconia (ZrO2-MgO, ZrO2 rare earths, etc.)
  • This catalytic reaction of methanol vapor reforming for the production of hydrogen is generally carried out in the gas phase (Belgian patent n ° 884,720, Japanese patent application n ° 59-128202 and French patent application n ° 86/17712) but also in phase liquid (French patent application n ° 87/02355).
  • This reaction according to reaction equations 1 and 2, gives rise to by-products, the most important of which are carbon dioxide (approximately 25% volume) and carbon monoxide (approximately 0.5 to 3% volume).
  • a system is known (for example US Pat. No. 4,553,981) based on the principle of selective adsorption under pressure of the constituents of a gas mixture, other than hydrogen, in the presence of adsorbent masses (molecular sieve, activated carbon, etc.). ) which is generally regenerated at room temperature, by depressurization and purging.
  • adsorbent masses molecular sieve, activated carbon, etc.
  • PSA Pressure Swing Adsorption
  • two minimum reactors of adsorbents are necessary: the first in the adsorption phase while the second is operated according to the different regeneration phases.
  • This process has the advantage of producing a hydrogen of very high purity (for example at least equal to 99.99%) and it is completely adapted to the operating pressure (for example 0.5 to 5 MPa) of the process of steam reforming of methanol, as described, for example in the present invention.
  • the hydrogen yield (hydrogen output / hydrogen input in percent) is quite low (70 to 80%) and incompatible in the state with the characteristics sought in the present invention (hydrogen yield compared to feed methanol at least equal to 95% ).
  • this yield decreases with the operating pressure; from around 80% at 3 MPa, it becomes around 70% at 1 MPa.
  • Japanese patent application No. 59 128202 proposes the recycling of part of the PSA purge (purge rich in hydrogen) upstream of the reactor. This device allows a 10 to 15% improvement in the hydrogen yield compared to the maximum yield (70 to 80%) indicated above for the PSA process coupled with methanol steam reforming, without recycling the PSA purge.
  • the new process proposed by the applicant makes it possible to simultaneously obtain a hydrogen of purity at least equal to 99.99% and a hydrogen yield at least equal to 95%, even if the reaction of methanol vapor reforming is carried out at relatively low pressure. , for example 0.8 to 2 MPa, although it is possible to operate under pressures of the order of 0.5 to 5 MPa, in an isothermal or adiabatic reactor, with axial or radial flow, operated in the gas phase or still in the presence of a liquid phase playing the role of heat transfer fluid.
  • the process which is the subject of the present invention is defined as follows:
  • the production of hydrogen is carried out by catalytic steam reforming of methanol, by reacting methanol and water under relatively high pressure on a catalyst for converting methanol into hydrogen. .
  • the gaseous effluent resulting from the reaction, after condensation of a portion of the unprocessed reactants is contacted with an adsorption agent, under relatively high pressure, so as to adsorb the by-products, including carbon dioxide, and to release a hydrogen-rich gas.
  • This adsorption agent is cyclically regenerated under relatively low pressure, releasing hydrogen and the by-products which had been adsorbed.
  • This desorption gas containing mainly hydrogen and carbon dioxide is subjected to a recompression and then to a treatment for removal, under relatively high pressure, of at least a portion of the carbon dioxide, before returning to the steam reforming zone.
  • methanol Decarbonation (removal of CO2) can be carried out by washing either with water and / or methanol of the charge or with an aqueous solution of amine or alkanolamine, for example an aqueous solution of mono and / or diethanolamine.
  • a solution for example, twice molar of diethanolamine to perform the gas washing at a pressure substantially equivalent to that of the methanol steam reforming reactor and at a temperature close to room temperature, for example 0-40 ° C and 0.5 to 5 MPa.
  • the solution obtained, before recycling to the washing tower, is regenerated by heating to a temperature of, for example, between 60 and 140 ° C., before depressurization at a pressure close to atmospheric pressure. Under these conditions, the rate of decarbonation of the gas can be between 95 and 99.9%.
  • the gaseous effluent from the decarbonation unit which contains for example 3 to 7% by volume of CO, is treated in a low temperature CO conversion reactor, according to reaction (3) above.
  • the gaseous effluent from this CO converter is then recycled, at least in part, at the inlet of the methanol steam reforming reactor.
  • this CO conversion reactor containing a bulk catalyst, based on copper associated with zinc and / or iron and optionally with aluminum and / or chromium
  • the operation is carried out between 160 and 300 °. C but preferably between 180 and 250 ° C, a pressure between 0.5 and 10 MPa but preferably between 0.9 and 4.5 MPa and with a H2O / C0 molar ratio between 1 and 30 but preferably 2 to 20.
  • the water necessary for the methanol vapor-reforming reaction, the mass ratio of H2O / CH3OH at the inlet of the reactor is defined above, can be introduced, in whole or in part, at the inlet of the conversion reactor CO, before recycling - a small part can however be purged.
  • This improved version of the process by conditions better suited to CO conversion: lower temperature, higher H2O / CO molar ratio, lower H2 and CO2 content, by lowering the CO content from a few percent to less than 1000 ppm (parts per million) , to increase, according to reaction (3) above, the hydrogen yield of the process.
  • the adsorption is most often carried out at 0.5 to 5 MPa of total pressure, and at a temperature of 20 to 50 ° C., for example.
  • Desorption is most often carried out under 0.1 to 0.4 MPa of total pressure.
  • Methanol (1) and water (2) reach the reactor (4) via line (3).
  • the reactor (4) also receives a recycling (5) of methanol and unconverted water and recycled gases (15) from the decarbonator (14).
  • the reactor effluent arrives via line (6) at the condenser (7) at the bottom of which a condensate is collected, part of which (5) is recycled and another part (8) is discharged as a purge.
  • the non-condensed gases are sent via line (9) to the adsorption device (10) of PSA type or the like. High purity hydrogen (11) is collected. Periodically, the conversion gases are sent to another adsorber, not shown, and the adsorbent is regenerated (purge) by depressurization and hydrogen sweeping.
  • a purge current (12) is thus collected which after passing through the compressor (13) reaches a unit (14) amine wash comprising washing and regenerating the amine solution.
  • the gas freed from at least the major part of CO2 is partly recycled (15) and partly discharged (16). After regeneration (removal of part of the CO2), the amine solution is recycled to the washing unit (14).
  • Figure 2 has the same elements as Figure 1, with the exception of the following: the reaction water is introduced in part or in whole (in whole in fig. 2) via line (18) instead of the pipe (2), and the decarbonated gas from the washing unit (14) added with this water passes through a CO converter (19) before reaching the pipes (15 and 16).
  • the purge (16) can represent 1 to 30%, preferably 1 to 10% by volume of the gas coming from the decarbonator (14) or from the converter (19); the balance is recycled (15).
  • the purge (8) represents, for example, 0.1 to 5% of the liquid effluent from the condenser (7), the balance being recycled (5).
  • the process of the invention therefore has the advantages of being able to produce both: - hydrogen of very high purity (greater than 99.99%) - with a yield greater than 95% which saves raw material (methanol) - even under relatively low pressure (around 1 MPa) which avoids the use of special materials, generally required to be able to work at higher pressure.
  • the diagram is that of FIG. 1; however the elements (13) to (17) are absent and the purge (12) is burned.
  • the hydrogen yield (R) defined by the relationship: is 66%.
  • the PSA purge (containing 30% of the hydrogen produced) is mixed with the gas which supplies the burners of the installation.
  • the diagram is that of FIG. 1; however elements 14 and 17 are absent.
  • the catalyst and the operating conditions of the steam reforming reactor are identical to those of Example 1 with the exception that it is recycled after recompression, the hydrogen-rich fraction of the PSA purge, the rest being removed.
  • This recycled fraction can represent approximately 40% by volume of the total purge and contain approximately 60% of the quantity of hydrogen contained in this purge.
  • the methanol vapor reforming reaction (4) and the purification (10) of the hydrogen produced (by PSA) are carried out according to the operating conditions of Example 1.
  • the PSA purge (12) instead of being burned , undergoes recompression to 1.1 MPa (13) then washing (14), with an aqueous solution of diethanolamine (4M) at 30 ° C at 1.1 MPa to remove 99% of carbon dioxide (17) and finally is recycled (15), at around 95%, at the inlet of the reactor. 5% are therefore eliminated as a purge (16).
  • the methanol vapor-reforming reaction, and the steps for purifying the hydrogen and decarbonating the PSA purge are carried out according to the conditions of Example 3.
  • this decarbonated purge may contain 5 to 10% by volume of oxide of carbon is sent, at 1.1 MPa, to a low temperature CO conversion reactor.
  • This reactor (19) contains 150 kg of copper catalyst (for example 50% Cu, 4% Al, 25% Zn); 10.9 kmol of water are injected (18) cocurrently with the purge gas.
  • the CO conversion reaction is carried out under 1.05 MPa, at an inlet temperature of 210 ° C., which makes it possible to convert 91% of the CO.
  • 95% of the gases from the CO conversion reactor are recycled to the methanol steam reforming reactor; 5% is eliminated in the drain (16). By doing so, the yield (R) of hydrogen of 99.99% purity is 95.9%.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
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  • Separation Of Gases By Adsorption (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP89401396A 1988-05-27 1989-05-22 Verfahren zur Erzeugung von Hochreinem Wasserstoff durch katalytische Reformierung von Methanol Expired - Lifetime EP0344053B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8807195 1988-05-27
FR8807195A FR2631949B1 (fr) 1988-05-27 1988-05-27 Procede de production d'hydrogene de haute purete par reformage catalytique du methanol

Publications (2)

Publication Number Publication Date
EP0344053A1 true EP0344053A1 (de) 1989-11-29
EP0344053B1 EP0344053B1 (de) 1992-03-04

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EP89401396A Expired - Lifetime EP0344053B1 (de) 1988-05-27 1989-05-22 Verfahren zur Erzeugung von Hochreinem Wasserstoff durch katalytische Reformierung von Methanol

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US (1) US5093102A (de)
EP (1) EP0344053B1 (de)
JP (1) JP2764178B2 (de)
BR (1) BR8902419A (de)
DE (1) DE68900907D1 (de)
FR (1) FR2631949B1 (de)
MX (1) MX171197B (de)

Cited By (1)

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FR2663625A1 (fr) * 1990-06-25 1991-12-27 Air Liquide Procede et installation d'elaboration d'hydrogene pur.

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DE19603222C1 (de) * 1996-01-30 1997-08-28 Daimler Benz Ag Verfahren und Vorrichtung zur Gewinnung eines wasserstoffreichen, kohlenmonoxidarmen Gases
DE19727588C1 (de) * 1997-06-28 1999-02-18 Dbb Fuel Cell Engines Gmbh Vorrichtung zur Erzeugung eines wasserstoffreichen und kohlenmonoxidarmen Gases
CN1110445C (zh) * 1999-02-04 2003-06-04 中国石化集团齐鲁石油化工公司 一种无残液排放的甲醇蒸汽转化制氢工艺
US6596423B2 (en) 2001-03-26 2003-07-22 Brookhaven Science Associates, Llc Method for low temperature catalytic production of hydrogen
CA2522401C (en) * 2003-04-16 2016-02-23 Energy & Environmental Research Center Foundation, Inc. System and process for producing high-pressure hydrogen
US20040253493A1 (en) * 2003-06-11 2004-12-16 Nissan Technical Center N. A. Inc. Reformate purifying system for fuel processing systems
JP4557849B2 (ja) * 2005-09-14 2010-10-06 株式会社東芝 エタノールからの水素製造方法
US7655394B2 (en) * 2005-10-28 2010-02-02 Boehringer Ingelheim International Gmbh Hepatitis C virus NS2/3 activity assay
JP4861729B2 (ja) * 2006-03-24 2012-01-25 石油コンビナート高度統合運営技術研究組合 水素製造方法および水素製造装置
FR2910457B1 (fr) * 2006-12-22 2009-03-06 Inst Francais Du Petrole Procede de purification par adsorption d'hydrogene avec cogeneration d'un flux de co2 en pression
FI20085400A0 (fi) * 2007-11-09 2008-04-30 Upm Kymmene Oyj Menetelmä jäteveden integroidulle käsittelylle
CN102923656B (zh) * 2012-11-12 2014-09-03 浙江大学 层叠式微凸台阵列型重整制氢微反应器
EP3156363A1 (de) * 2015-10-15 2017-04-19 Casale SA Verfahren zur herstellung von synthesegas durch reformieren eines kohlenwasserstoffs mit rückgewinnung von kohlendioxid unter hohem druck
EP3863962B1 (de) * 2018-10-12 2023-10-04 UPM-Kymmene Corporation Verfahren zur herstellung von wasserstoff
CN110694624B (zh) * 2019-10-10 2022-07-19 天津大学 一种基于Cu和MgO的双功能催化剂及制备方法和应用
CN115057412A (zh) * 2022-06-13 2022-09-16 新疆天业汇合新材料有限公司 利用甲醇合成反应脱除co、co2提高氢气纯度的方法
CN115465836B (zh) * 2022-09-05 2023-07-25 福建永荣科技有限公司 一种甲醇制氢工艺
TWI831412B (zh) * 2022-10-12 2024-02-01 中興電工機械股份有限公司 一體化產氫充氫系統及其方法

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EP0159495A2 (de) * 1984-03-10 1985-10-30 BASF Aktiengesellschaft Verfahren zum Entfernen von C02 und/oder H2S aus Gasen
EP0272182A1 (de) * 1986-12-16 1988-06-22 Institut Français du Pétrole Verfahren zur Erzeugung von Methanol durch Dampfreformierung

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EP0159495A2 (de) * 1984-03-10 1985-10-30 BASF Aktiengesellschaft Verfahren zum Entfernen von C02 und/oder H2S aus Gasen
EP0272182A1 (de) * 1986-12-16 1988-06-22 Institut Français du Pétrole Verfahren zur Erzeugung von Methanol durch Dampfreformierung

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CHEMICAL ABSTRACTS, vol. 108, no. 6, février 1988, page 157, résumé no. 40558t, Columbus, Ohio, US; & JP-A-62 246 803 (MITSUBISHI GAS CHEMICAL CO. INC.) 28-10-1987 *
CHEMICAL ABSTRACTS, vol. 94, no. 18, 4 mai 1981, page 132, résumé no. 141951p, Columbus, Ohio, US; T. YAMAMOTO: "Manufacture of hydrogen - methanol steam reforming and PSA method", & KAGAKU SOCHI 1980, 22(11), 11-18 *
PATENT ABSTRACTS OF JAPAN, vol. 8, no. 246 (C-251)[1683], 10 novembre 1984, page 152 C 251; & JP-A-59 128 202 (NIHON KAGAKU GIJUTSU K.K.) 24-07-1984 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2663625A1 (fr) * 1990-06-25 1991-12-27 Air Liquide Procede et installation d'elaboration d'hydrogene pur.
EP0465298A1 (de) * 1990-06-25 1992-01-08 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Verfahren und Anlage zur Herstellung eines gasförmigen Bestandteils aus einer gasförmigen Mischung
US5137547A (en) * 1990-06-25 1992-08-11 L'air Liquide, Societe Anonyme Pour L'exploitation Des Procedes Georges Claude Process and apparatus for preparing a gas component from a gas mixture

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JPH01305801A (ja) 1989-12-11
MX171197B (es) 1993-10-06
BR8902419A (pt) 1990-01-16
DE68900907D1 (de) 1992-04-09
US5093102A (en) 1992-03-03
EP0344053B1 (de) 1992-03-04
JP2764178B2 (ja) 1998-06-11
FR2631949B1 (fr) 1990-09-14
FR2631949A1 (fr) 1989-12-01

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